CN108554411B - Composite carrier loaded nickel-based catalyst for preparing synthesis gas by reforming methane with pressurized carbon dioxide - Google Patents
Composite carrier loaded nickel-based catalyst for preparing synthesis gas by reforming methane with pressurized carbon dioxide Download PDFInfo
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Abstract
The invention discloses a composite carrier loaded nickel-based catalyst for preparing synthesis gas by reforming methane with pressurized carbon dioxide, wherein the carrier of the catalyst is SiO2、Al2O3、TiO2At least two of the components, wherein the active components are Ni, Ni-Fe or Ni-Co, the content of the active components is 5-20 percent based on the mass of the catalyst as 100 percent, and the rest is a carrier; the catalyst is prepared by taking glycine, alanine, threonine, citric acid, oxalic acid and the like as coordination-combustion promoters by adopting a coordination-decomposition method, and has the advantages of simple preparation process, low cost, economy and environmental protection. The catalyst has higher methane and carbon dioxide conversion rate for reforming methane by carbon dioxide under the pressurization condition, and shows high activity, high stability and extremely high anti-carbon deposition and anti-sintering capacity.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a composite carrier loaded nickel-based catalyst for preparing synthesis gas by reforming methane with carbon dioxide under a pressurized condition.
Background
In recent years, as people have been increasingly aware of the greenhouse effect, CO, which is one of the strongest greenhouse gases2Capture and its use have attracted increasing attention. Carbon dioxide reforming catalystThe alkane can utilize CO simultaneously2And CH4Two kinds of greenhouse gases have great significance for reducing emission of greenhouse gases, and H of synthesis gas2the/CO is less than or equal to 1, and can be used as raw material gas for synthesizing carbonyl and organic oxygen-containing compounds. After the research on carbon dioxide reformed methane was reported by Ashcroft et al (nat. chem.,1991,352: 225-.
Catalyst systems for reforming methane with carbon dioxide are mainly divided into two types, one type is a catalyst taking precious metal (Pt, Rh, Ru, Pd and Ir) as an active component, and although the catalyst has high activity, selectivity and stability, the source of the catalyst is limited, the price is high, and the catalyst is difficult to realize commercial application. Another class is catalysts with non-noble group VIII metals (Fe, Ni, Co) as the active components, in the order of Ni > Co > Fe, where Ni-based catalysts are widely regarded for high catalytic activity and low cost. However, the Ni-based catalyst also has the disadvantages of easy carbon deposition and sintering, resulting in a decrease in catalytic activity. Therefore, the hot spot of reforming methane with carbon dioxide is mainly focused on how to improve the stability and the anti-carbon deposition performance of the Ni-based catalyst. Theoretical research shows that the nucleation and growth of fiber carbon can be inhibited only by smaller Ni particle size, thereby achieving the purpose of carbon deposition resistance. In practical application, the Ni-based catalyst is usually prepared by adopting an impregnation method, a precipitation method or a sol-gel method, the catalyst prepared by the methods can keep better catalytic activity and stability in a short period, but active components are easy to agglomerate and sinter and are easy to lose activity due to carbon deposition in the long-period carbon dioxide reforming methane reaction operation.
The reforming of methane with carbon dioxide requires high temperature reaction, so the carrier selected for the nickel-based catalyst must have good thermal stability, such as Al2O3、SiO2、MgO、MgO-Al2O3、CeO2-ZrO2And mesoporous molecular sieves, ceramic foams, and the like. In addition, most of the currently developed nickel-based catalysts take the reaction of reforming methane with carbon dioxide under normal pressure as a probe reaction, the storage and transportation of natural gas are under high pressure conditions, and the conversion technology (such as Fischer-Tropsch synthesis reaction and methanol synthesis) also takes synthesis gas as a sourceIs achieved at a higher pressure, so that the methane reforming process under pressurized conditions is more reasonable and efficient from the overall energy efficiency perspective. From the analysis of dynamics, the reaction rate is more favorable to be improved under the pressurizing condition, and the carbon deposition rate and the carbon elimination rate on the surface of the catalyst are also increased. When the rate of carbon deposition on the surface of the catalyst is greater than the rate of carbon deposition removal, the catalyst will accelerate carbon deposition deactivation and even plug the bed layer to terminate the reaction.
The research group (Ind. Eng. chem. Res.2014,53, 19077-19086; int. J. of hydrogen energy 2014,39,11592-11605) of the inventor prepares Ni/SiO by using a combustion decomposition method with carboxylic acid or amino acid as a complexing agent2When the reaction pressure is increased from 1.0atm to 10atm, the carbon deposit amount of the catalyst is increased from 2.0 wt% to 80 wt% after 20h of reaction, although the catalyst has a certain carbon holding capacity, the carbon deposit amount gradually increases, once the carbon deposit amount exceeds the carbon holding capacity of the catalyst, the catalyst is rapidly deactivated, and the bed layer is blocked by the carbon deposit, so that the reaction has to be stopped.
It can be seen from the above that, the carbon deposition of the catalyst which can be developed under normal pressure and can stably operate in the reaction of reforming methane with carbon dioxide is particularly serious under the pressurized condition, so that the catalyst bed layer is blocked by the carbon deposition, and the reaction of reforming methane with carbon dioxide cannot be continued. Therefore, it is currently the focus of research to obtain a carbon dioxide reforming methane reaction catalyst having high activity and resistance to carbon deposition under pressurized conditions.
Disclosure of Invention
The invention aims to overcome the defect that the carbon dioxide reforming methane catalyst is easy to deposit carbon to cause inactivation under the pressurizing condition, and provides the composite carrier loaded nickel-based catalyst for preparing the synthesis gas by reforming the methane with the carbon dioxide, which has high activity and good stability under the pressurizing condition.
The carrier of the catalyst used for solving the technical problems is SiO2、Al2O3、TiO2At least two of them, active components are Ni, Ni-Fe or Ni-Co, and the mass of the catalyst is 100 percent, and the content of the active components is5-20 percent of carrier and the balance of carrier; the catalyst is prepared by the following method:
according to the composition of the catalyst, an active component precursor and a carrier precursor are dissolved in ethanol, then an aqueous solution of a coordination-combustion improver is added, the mixture is stirred for 2-4 hours at room temperature, a solvent is evaporated to obtain a viscous liquid, the liquid is heated and combusted, solid powder obtained by combustion is uniformly ground, the mixture is roasted for 3-6 hours in an air atmosphere at 550-800 ℃, and is naturally cooled to room temperature, tableted and granulated, and then the catalyst is screened by a 40-60-mesh sieve, so that the catalyst is obtained.
The coordination-combustion improver is any one of glycine, alanine, threonine, serine, ethylenediamine, citric acid, urea, trimesic acid, nicotinic acid and oxalic acid, preferably any one of glycine, alanine and threonine; the addition amount of the coordination-combustion improver is 0.5 to 2 times, preferably 1 to 1.5 times of the total molar amount of the metal element in the active component precursor and the metal element and the metalloid element (Si is the metalloid element) in the carrier precursor.
In the above catalyst, the content of the active component is preferably 10% by mass of the catalyst of 100%.
When the active component is Ni, the precursor of the active component is nickel nitrate or nickel oxalate; when the active component is Ni-Fe, the precursor of the active component is a mixture of any one of nickel nitrate and nickel oxalate and any one of ferric nitrate, ferric oxalate and ammonium ferric citrate; when the active component is Ni-Co, the precursor of the active component is a mixture of any one of nickel nitrate and nickel oxalate and any one of cobalt nitrate, cobalt acetylacetonate and cobalt oxalate.
The carrier precursor is SiO2Precursor and Al2O3Precursor, TiO2At least two of the precursors, wherein SiO2The precursor is any one of methyl silicate, ethyl orthosilicate, propyl silicate and butyl silicate, and Al2O3The precursor is any one of aluminum isopropoxide, aluminum nitrate and pseudo-boehmite, and TiO2The precursor is any one of tetrabutyl titanate and titanium isopropoxide.
In the above method for preparing the catalyst, it is further preferable to calcine the catalyst in an air atmosphere at 650 to 750 ℃ for 3 to 6 hours.
The invention has the following beneficial effects:
1. the invention adopts a coordination-decomposition method, in the preparation process of the catalyst, the coordination-combustion improver can coordinate with metal cations in an active component precursor and a carrier precursor to form a complex, the high dispersion of the metal cations can be ensured in the evaporation and rapid combustion processes of a solvent, and the strong interaction between metal and the carrier is formed, so that the active metal is not easy to migrate and gather in the high-temperature reaction, the dispersion degree and the surface active metal content of the active metal are improved, and small metal particles are kept, thereby improving the high-temperature activity and the stability of the catalyst.
2. In the catalyst, the active component has the particle size of about 4.0-10 nm, smaller particle size and narrower distribution, is beneficial to inhibiting the generation of carbon deposition on the surface of the catalyst, has higher methane and carbon dioxide conversion rate on the methane reformed by carbon dioxide under the pressurization condition, and shows high activity, high stability and extremely high carbon deposition resistance and sintering resistance.
3、SiO2The porous Ni-Ni alloy has a good pore structure and a large specific surface area, but has weak interaction with metal Ni, and is easy to sinter and agglomerate; al (Al)2O3Has good heat resistance and high melting point, but is easy to form nickel aluminate spinel after high-temperature treatment, thereby causing difficult reduction, and Al2O3The surface is acidic, and the surface carbon deposition of the catalyst is easily caused in the dry reforming reaction of methane; TiO 22Has N-type semiconductor property, has strong electronic interaction with nickel metal, and is helpful for adsorbing and activating CO2And the oxygen-containing acids such as carbonate are formed, so that the coordination-combustion improver is coordinated with metal cations in the carrier precursor by compounding the precursors of the carriers in the preparation process of the catalyst to form the composite carrier with uniformly distributed components. Wherein, the acid-base property of the carrier surface, the interaction between the active component and the carrier, the electron cloud density of the nickel metal atom and the like are modulated by controlling the proportion of the components, the advantages of the carriers are fully utilized, and the nickel metal atom and the carrier generate electron cloudThe activity, the carbon deposition resistance and the stability of the catalyst are obviously improved due to the synergistic effect.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 20 percent of Al2O3-70％SiO21.63g (5.6054mmol) of nickel nitrate hexahydrate, 2.6360g (12.9063mmol) of aluminum isopropoxide and 7.9853g (38.3301mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give solution A. 7.1655g (56.8418mmol) of oxalic acid dihydrate were dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 2
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 20 percent of TiO2-70％SiO21.63g (5.6054mmol) of nickel nitrate hexahydrate, 2.8035g (8.2379mmol) of tetrabutyl titanate and 7.9853g (38.3301mmol) of ethyl orthosilicate are dissolved in 40g of ethanol to give solution A. 10.9637g (52.1734mmol) of citric acid monohydrate were dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 3
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 20 percent of TiO2-70％Al2O31.63g (5.6054mmol) of nickel nitrate hexahydrate, 2.8035g (8.2379mmol) of tetrabutyl titanate and 9.2260g(45.1721mmol) of aluminum isopropoxide was dissolved in 40g of ethanol to give solution A. 4.4303g (59.0154mmol) of glycine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 4
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 20 percent of SiO2-70％Al2O31.63g (5.6054mmol) of nickel nitrate hexahydrate, 2.2815g (10.9515mmol) of ethyl orthosilicate and 9.2260g (45.1721mmol) of aluminum isopropoxide were dissolved in 40g of ethanol to give solution A. 5.4994g (61.7290mmol) of alanine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 5
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 20 percent of Al2O3-70％TiO21.63g (5.6054mmol) of nickel nitrate hexahydrate, 2.6360g (12.9063mmol) of aluminum isopropoxide and 9.8124g (28.8328mmol) of tetrabutyl titanate were dissolved in 40g of ethanol to give solution A. 5.6397g (47.3445mmol) of threonine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 6
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 20 percent of SiO2-70％TiO21.63g (5.6054mmol) of nickel nitrate hexahydrate, 2.2815g (10.9515mmol) of ethyl orthosilicate and 9.8124g (28.8328mmol) of tetrabutyl titanate were dissolved in 40g of ethanol to give a solution A. 5.1111g (45.3897mmol) of glycine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 7
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 30 percent of Al2O3-30％TiO2-30％SiO21.63g (5.6054mmol) of nickel nitrate hexahydrate, 3.9540g (19.3595mmol) of aluminum isopropoxide, 4.2053g (12.3569mmol) of tetrabutyl titanate, 3.4223g (16.4272mmol) of ethyl orthosilicate are dissolved in 40g of ethanol to give solution A. 4.7885g (53.7490mmol) of alanine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 8
According to the catalyst composition, the catalyst comprises 12 percent of Ni-3Fe percent to 25 percent of Al2O3-30％TiO2-30％SiO21.956g (6.7242mmol) of nickel nitrate hexahydrate, 0.7139g (1.7671mmol) of iron nitrate nonahydrate, 3.2950g (16.1329mmol) of aluminum isopropoxide, 4.2053g (12.3569mmol) of tetrabutyl titanate, 3.4223g (16.4272mmol) of ethyl orthosilicate are dissolved in 40g of ethanol to give solution A. 4.0094g (53.4083mmol) of glycine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring at room temperature for 4 hours, and evaporating the solvent by using a rotary evaporatorAnd transferring the obtained viscous liquid to an electric heating furnace for combustion, placing solid powder obtained by combustion in a muffle furnace for roasting, heating to 700 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving with a 40-60-mesh sieve to prepare the catalyst.
Example 9
According to the catalyst composition, the catalyst comprises 12 percent of Ni-3Co percent to 25 percent of Al2O3-30％TiO2-30％SiO21.956g (6.7265mmol) of nickel nitrate hexahydrate, 0.4874g (1.6748mmol) of cobalt nitrate hexahydrate, 3.2950g (16.1329mmol) of aluminum isopropoxide, 4.2053g (12.3569mmol) of tetrabutyl titanate and 3.4223g (16.4272mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to obtain solution A. 4.0026g (53.3183mmol) of glycine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
In order to prove the beneficial effects of the invention, the inventor uses the catalysts prepared in examples 1-9 in the reaction of catalyzing carbon dioxide to reform methane, and the specific test method is as follows:
0.15g of catalyst was placed in a fixed bed reactor and H was fed2And N2The volume ratio of the mixed gas to the mixed gas is 2:8, and the flow rate is 50 mL/min-1At 4 ℃ in min-1The temperature rising rate of (2) was increased from room temperature to 700 ℃ and reduced for 2.5 hours. Subsequently, H is turned off2Continuing to introduce N2At 2 ℃ min-1The temperature rises to 750 ℃ at a temperature rising rate, and after the temperature is stabilized, the reaction gas (CO) is switched to2And CH4Mixed gas of (1: 1) by volume), the total amount of the reaction gas is 130 mL. min-1CO at P ═ 1.0MPa and T ═ 750 deg.C2/CH41.0, 53200mL g-1·h-1Reacting under the condition, and enabling the reacted gas to pass through a chromatograph of a GC9560 type thermal conductivity cell detector in Shanghai HuaaiThe detection and analysis are carried out by an instrument (chromatographic columns are 5A and PQ columns), and the experimental results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the catalyst of the present invention has high methane and carbon dioxide conversion rates under pressurized conditions for reforming methane with carbon dioxide, and CO is at 1.0MPa and 750 ℃ C2/CH41.0, 53200mL g-1·h-1Under the condition, when the content of Ni or Ni-Fe or Ni-Co in the catalyst is 10%, the initial conversion rate of methane can reach more than 48%, the initial conversion rate of carbon dioxide can reach more than 69%, the service life of the catalyst is long, the stability is high, and the activity is basically stable and unchanged after continuous reaction for 60 hours.
Claims (5)
1. A composite carrier load nickel-based catalyst for preparing synthesis gas by pressurizing carbon dioxide reforming methane is characterized in that: the carrier of the catalyst is SiO2、Al2O3、TiO2At least two of the components, wherein the active components are Ni, Ni-Fe or Ni-Co, the content of the active components is 5-20 percent based on the mass of the catalyst as 100 percent, and the rest is a carrier; the catalyst is prepared by the following method:
dissolving an active component precursor and a carrier precursor in ethanol according to the composition of the catalyst, then adding a coordination-combustion improver aqueous solution, stirring for 2-4 hours at room temperature, evaporating to remove a solvent to obtain a viscous liquid, heating and burning the liquid, uniformly grinding solid powder obtained by burning, roasting for 3-6 hours in an air atmosphere of 650-750, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60-mesh sieve to obtain the catalyst;
the coordination-combustion improver is any one of glycine, alanine, threonine, citric acid and oxalic acid, and the addition amount of the coordination-combustion improver is 1.0-1.5 times of the total molar amount of metal elements in the active component precursor and metal elements and metalloid elements in the carrier precursor.
2. The composite carrier-supported nickel-based catalyst for pressurized carbon dioxide reforming of methane to synthesis gas according to claim 1, wherein: the content of active components was 10% based on 100% by mass of the catalyst.
3. The composite carrier-supported nickel-based catalyst for pressurized carbon dioxide reforming of methane to synthesis gas according to claim 1 or 2, wherein: the coordination-combustion improver is any one of glycine, alanine and threonine.
4. The composite carrier-supported nickel-based catalyst for pressurized carbon dioxide reforming of methane to synthesis gas according to claim 1, wherein: when the active component is Ni, the precursor of the active component is nickel nitrate or nickel oxalate; when the active component is Ni-Fe, the precursor of the active component is a mixture of any one of nickel nitrate and nickel oxalate and any one of ferric nitrate, ferric oxalate and ammonium ferric citrate; when the active component is Ni-Co, the precursor of the active component is a mixture of any one of nickel nitrate and nickel oxalate and any one of cobalt nitrate, cobalt acetylacetonate and cobalt oxalate.
5. The composite carrier-supported nickel-based catalyst for pressurized carbon dioxide reforming of methane to synthesis gas according to claim 1, wherein: the carrier precursor is SiO2Precursor and Al2O3Precursor, TiO2At least two of the precursors, wherein SiO2The precursor is any one of methyl silicate, ethyl orthosilicate, propyl silicate and butyl silicate, and Al2O3The precursor is any one of aluminum isopropoxide, aluminum nitrate and pseudo-boehmite, and TiO2The precursor is any one of tetrabutyl titanate and titanium isopropoxide.
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| CN110270377B (en) * | 2019-07-01 | 2022-10-18 | 西京学院 | Methane dry reforming nickel-based catalyst and preparation method and application thereof |
| CN110404545B (en) * | 2019-08-07 | 2022-06-07 | 西京学院 | Nickel-based catalyst for preparing synthesis gas by reforming methane-carbon dioxide, method and application |
| CN111495373B (en) * | 2020-04-22 | 2023-03-10 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing glycine methyl ester and glycine from methyl glycolate by using double-metal glass wire layered eutectic |
| CN112403470B (en) * | 2020-11-25 | 2023-07-14 | 陕西榆大科技发展有限公司 | Catalyst for preparing synthetic gas by reforming methane and carbon dioxide and application thereof |
| CN113559836A (en) * | 2021-08-12 | 2021-10-29 | 西北大学 | High-efficiency supported bimetallic catalyst, preparation method and application |
| CN113751018A (en) * | 2021-09-28 | 2021-12-07 | 石家庄迪飞科技有限公司 | Preparation method of efficient combustion catalyst for VOCs (volatile organic compounds) |
| CN114192130B (en) * | 2021-11-30 | 2023-10-27 | 陕西师范大学 | Preparation method of spiral transition metal nanotube catalyst |
| CN116272994A (en) * | 2022-12-21 | 2023-06-23 | 浙江工业大学 | Catalyst suitable for catalyzing hydrogenation of carbon dioxide to prepare high-carbon hydrocarbon, and preparation method and application thereof |
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